Project/Area Number |
10650870
|
Research Category |
Grant-in-Aid for Scientific Research (C)
|
Allocation Type | Single-year Grants |
Section | 一般 |
Research Field |
高分子合成
|
Research Institution | Osaka Prefecture University |
Principal Investigator |
TSUNOOKA Masahiro College of Engineering, Professor, 工学部, 教授 (50081328)
|
Project Period (FY) |
1998 – 1999
|
Project Status |
Completed (Fiscal Year 1999)
|
Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1999: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1998: ¥2,000,000 (Direct Cost: ¥2,000,000)
|
Keywords | acyloxyimino groups / photobase generator / photo-crosslinking / crosslinking / quinone / benzophenone / carbamoyloxyimino group / sensitization / 増感基 / ベンゾキノン / ナフトキイン |
Research Abstract |
1.Copolymers bearing acyloxyimino (AOI) groups were prepared by the use of aceophenone O-acryloyloxime and comonomers (e.g.styrene). AOI groups in their films are transformed into amino groups upon UV irradiation. The irradiated films are soluble in organic solvents. When the films with quinones such as 1,4-benzoquinone, 1,4-naphthoquinone and 2-dodecylthio-1,4-benzoquinone were irradiated, the films became insolale in organic solvents and the degree of the insoluble fraction increased with thermal treatment above their glass transition temperature. The photo-crosslinking was found to be induced by the reaction of polymer radicals with quinones and the thermal crosslinking to be due to the reaction of pendant amino groups with quinones. 2. UV irradiation of copolymers bearing both AOI groups and sensitizing groups such as benzophenone units in films induced their insolublization and the post-baking also was effective for the enhancement of the degree of insolublization. The photo-crossl
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inking was clarified to be induced by the polymer radicals formed by the hydrogen-abstraction of the excited benzophenone units and the thermal crosslinking to be due to the association of resulting amino groups. However, the details of mechanism of the thermal crosslinking is not clear. 3. Photo-irradiation of copolymers bearing carbamoyloxyimino groups in films was found to induce their insolublization with the formation of pendant amino and hydrazino groups. Furthermore, the degree of the insolubilization was enhanced by the thermal treatment after the irradiation. The results from No1 to No3 are very interesting as the novel photo-crosslinking systems which can be amplified thermally. 4.We have found that the photolysis of quaternary ammonium salts bearing phenacyl groups and N,N-dimethylcarbamate anion results in the formation of tert-amines. This is the novel photobase generators different from photobase generator which generate photochemically primary and secondary amines. Their use in anionic polymerization and curing of epoxides are expected. Less
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